Synthesis and evaluation of a novel fluorescent photoprobe for imaging matrix metalloproteinases

Faust, A; Waschkau, B; Waldeck, J; Holtke, C; Breyholz, HJ; Wagner, S; Kopka, K; Heindel, W; Schafers, M; Bremer, C

HERO ID

184678

Reference Type

Journal Article

Year

2008

Language

English

PMID

18396900

HERO ID 184678
In Press No
Year 2008
Title Synthesis and evaluation of a novel fluorescent photoprobe for imaging matrix metalloproteinases
Authors Faust, A; Waschkau, B; Waldeck, J; Holtke, C; Breyholz, HJ; Wagner, S; Kopka, K; Heindel, W; Schafers, M; Bremer, C
Journal Bioconjugate Chemistry
Volume 19
Issue 5
Page Numbers 1001-1008
Abstract The measurement of matrix metalloproteinase (MMP) activity in diseases like inflammation, oncogenesis, or atherosclerosis in vivo is highly desirable. Fine-tuned pyrimidine-2,4,6-triones (barbiturates) offer nonpeptidyl lead structures for developing imaging agents for specifically visualization of activated MMPs in vivo. The aim of this study was to modify a C-5-disubstituted barbiturate and thus design a highly affine, nonpeptidic, optical MMP inhibitor (MMPI)-ligand for imaging of activated MMPs in vivo. A convergent 10 step synthesis was developed, starting with a malonic ester and (4-bromophenoxy)benzene to generate 5-bromo-pyrimidine-2,4,6-trione as the key intermediate. To minimize the interactions between activated MMPs and the dye of the conjugate 6, a PEGylated piperazine derivative was used as a spacer and an azide as a protected amino function. After linking both building blocks, reducing the azide ( Staudinger reaction) and labeling with Cy 5.5, we obtained the nonhydroxamate MMP inhibitor 6 with high affinity (IC 50-value: 48 nM for MMP-2) measured in a fluorogenic assay using commercially available MMP-substrates and the purified enzyme. Zymography revealed an efficient blocking of enzyme activity of purified MMP-2 and MMP-9 and of MMP-containing cell supernatants (HT-1080), (A-673) using the PEGylated barbiturate 5. Fluorescence microscopy studies using a highly (A-673) and a moderate (HT-1080) MMP-2 secreting cell line showed efficient binding of the Cy 5.5 labeled tracer 6 to the MMP-2 positive cells while MMP-2 negative cells (MCF-7) did not bind. Therefore, this new barbiturate-based MMP-probe has a high affinity and specificity toward MMP-2 and -9 and is thus a promising candidate for sensitive MMP detection in vivo.
Doi 10.1021/bc700409j
Pmid 18396900
Wosid WOS:000256105100004
Url https://www.proquest.com/scholarly-journals/synthesis-evaluation-novel-fluorescent-photoprobe/docview/216188394/se-2?accountid=171501
Is Certified Translation No
Dupe Override No
Is Public Yes
Language Text English
Keyword *Barbiturates/cs [Chemical Synthesis]; *Barbiturates/ch [Chemistry]; Barbiturates/pd [Pharmacology]; Binding Sites; Binding, Competitive; Blotting, Western; Diagnostic Imaging; *Fluorescent Dyes/cs [Chemical Synthesis]; *Fluorescent Dyes/ch [Chemistry]; Fluorescent Dyes/pd [Pharmacology]; Humans; Ligands; Matrix Metalloproteinase 2/ai [Antagonists & Inhibitors]; *Matrix Metalloproteinase 2/ch [Chemistry]; Matrix Metalloproteinase 2/me [Metabolism]; Matrix Metalloproteinase 9/ai [Antagonists & Inhibitors]; *Matrix Metalloproteinase 9/ch [Chemistry]; Matrix Metalloproteinase 9/me [Metabolism]; Microscopy, Fluorescence/mt [Methods]; Molecular Structure; Polymerase Chain Reaction/mt [Methods]; Protease Inhibitors/cs [Chemical Synthesis]; Protease Inhibitors/ch [Chemistry]; Protease Inhibitors/pd [Pharmacology]; Sensitivity and Specificity; Structure-Activity Relationship; Tumor Cells, Cultured; 0 (Barbiturates); 0 (Fluorescent Dyes); 0 (Ligands); 0 (Protease Inhibitors); EC 3-4-24-24 (Matrix Metalloproteinase 2); EC 3-4-24-35 (Matrix Metalloproteinase 9)
Is Peer Review Yes
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